Branched oligoarylsilanes and synthesis method thereof

FIELD: chemistry.

SUBSTANCE: invention relates to novel branched oligoarylsilanes and their synthesis method. The engineering problem is obtaining branched oligoarylsilanes which contain not less than 5 functional arylsilane links and have a set of properties which enable their use as luminescent materials. The disclosed branched oligoarylsilanes have general formula where R denotes a substitute from: straight or branched C1-C20 alkyl groups; straight or branched C1-C20 alkyl groups separated by at least one oxygen atom; straight or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20 alkenyl groups; Ar denotes identical or different arylene or heteroarylene radicals selected from: substituted or unsubstituted thienyl-2,5-diyl, substituted or unsubstituted phenyl-1,4-diyl, substituted or unsubstituted 1,3-oxazole-2,5-diyl, substituted fluorene-4,4'-diyl, substituted cyclopentadithiophene-2,7-diyl; Q is a radical selected from the same group as Ar; X is at least one radical selected from the same group as Ar and/or a radical selected from: 2,1,3-benzothiodiazole-4,7-diyl, anthracene-9,10-diyl, 1,3,4-oxadiazole-2,5-diyl, 1-phenyl-2-pyrazoline-3,5-diyl, perylene-3,10-diyl; L equals 1 or 3 or 7 and preferably 1 or 3; n is an integer from 2 to 4; m is an integer from 1 to 3; k is an integer from 1 to 3. The method of obtaining branched oligoarylsilanes involves reaction of a compound of formula where Y is a boric acid residue or its ester or Br or I, under Suzuki reaction conditions with a reagent of formula (IV) A - Xm - A (IV), where A denotes: Br or I, provided that Y denotes a boric acid residue or its ester; or a boric acid residue or its ester, provided that Y denotes Br or I.

EFFECT: obtaining novel compounds distinguished by high luminescence efficiency, efficient intramolecular transfer of energy between molecule fragments and high thermal stability.

24 cl, 12 dwg, 1 tbl, 11 ex

 

The invention relates to the field of chemical technology organosilicon compounds and can find industrial application in obtaining new functional materials with luminescent properties. More specifically, the invention relates to novel branched oligoanilines and the way they are received.

Under extensive oligoaniline in this invention we understand such oligoaniline, which are highly ordered spatial hyperbranched fully acyclic education (Fig. 1, 2). In this invention, these molecules get Paladino. To do this, first get "branches", which are called monumentally and contain a single functional group at the focal point (figure 3). The resulting monodendri attached to bifunktionalnomu Allenova or heteroarenes center education oligoanilines. The original monodendri can be obtained as convergent and divergent method.

Unlike conventional polymers, branched oligoaniline, in the framework of this invention are the individual compounds, which allows them to allocate a purity available for low molecular weight compounds. This is especially important for organic electronics and Photonics. Specific three-dimensional architecture is ur such macromolecules gives them also a number of valuable properties, such as good solubility and film formation, in combination with the possibility to adjust their optical and electrical properties by targeted molecular design.

Under kilcranny in this invention refers to compounds that have a direct connection to the silicon-aryl or silicon-heteroaryl. Known linear and branched ailinani, as well as linear and branched polymers with arislanova fragments in the main chain or as lateral substituents.

Extensive oligoaniline described in the framework of this invention, similar in structure to organic dendrimers. Organic light-emitting dendrimers and devices based on them are known, for example, from European patent EP 1027398 B1, 2004, U.S. Patent US 6558818 B1, 2003 and US 6720093 B2, 2004. Used dendrimers may contain silicon fragments, and heteroarenes. However, the synthesis of dendrimers time-consuming and costly process.

The closest in structure to the claimed branched oligoaniline is oligoarticular And having the following structural formula (Adv. Funct. Mater. 2005. 15. 1799-1805.):

which can be represented by the General formula (a-1):

.

Extensive oligoaniline A, in contrast to the stated aliguori the silanes, contains four phenyl fragment attached to the silicon atom. It is known that the synthesis chetyrehzaryadnyh arrelano difficult. In the framework of this invention are claimed molecules containing Transnistria ailinani, which greatly simplifies the receipt of such molecules. In addition, the claimed compounds, in contrast to the known, contain end groups R, which significantly improve the solubility oligoanilines.

The task of the claimed invention to provide a new technical result consists in the synthesis of novel branched oligoanilines containing at least five functional arrelano links with a set of properties for their use as luminescent materials for organic electronics and Photonics. As such, the properties within this invention are the high luminescence efficiency, efficient intramolecular energy transfer from one of the fragments of the molecule to the other and high thermal stability.

In addition, the object of the invention is to develop a new method of obtaining the claimed branched oligoanilines, allowing you to get the products given the structure of high purity and suitable for use in an industrial environment.

The task is solved in that the obtained branched, oligoamine the Ana General formula (I)

where R is the Deputy of a range of: linear or branched C1-C20alkyl group; a linear or branched C1-C20alkyl groups separated by at least one oxygen atom; a linear or branched C1-C20alkyl groups separated by at least one sulfur atom; a branched C3-C20alkyl groups separated by at least one atom of silicon; C2-C20alkeneamine group,

Ar represents the same or different allenbyi or heteroarenes radicals selected from the series of: substituted or unsubstituted thienyl-2,5-diyl General formula (II-a)

substituted or unsubstituted phenyl-1,4-diyl General formula (II-b)

substituted or unsubstituted 1,3-oxazol-2,5-diyl General formula (II-b)

substituted fluoren-4,4'-diyl General formula (II-g)

substituted cyclopentadiene-2,7-diyl General formula (II-d)

where R1, R2, R3, R4, R5independently from each other denote H or Deputy of the above series for R; R6, R7, R8, R9means the Deputy of the above series for R,

Q means adical of the above number for Ar,

X represents at least one radical selected from the above number for Ar and/or a radical from the series: 2,1,3-benzothiadiazole-4,7-diyl General formula (II-e)

anthracene-9,10-diyl formula (II-f)

1,3,4-oxadiazol-2,5-diyl General formula (II-C)

1-phenyl-2-pyrazolin-3,5-diyl General formula (II)

perylene-3,10-diyl General formula (II-K)

.

L is 1 or 3 or 7, preferably 1 or 3;

n means an integer from the range from 2 to 4;

m means an integer from the range from 1 to 3;

k denotes an integer from the range from 1 to 3.

When this fragment Xm(Qk)2is the inner part of the molecule and the length of this fragment is determined by the values of m and k; and the outer part of the molecule consists of two blocks containing L repetitive fragments

that end fragments of R, the number of which is equal to (L+1). It should be noted that the silicon atoms are points of discontinuity mates (Organometallics 2007, 26, 5165-5173.) as between the inner and outer parts of the molecule, and between the individual pieces that make up the outer part of the molecule. The length of the coupling oligoanilines fragment in the inner part of the molecule is greater than the length of any pair is C oligoaniline fragments in the outer part of the molecule, that ensures efficient energy transfer from the external to the internal portion of the molecule. To implement such an effective energy transfer requires that the luminescence spectrum oligoaniline fragments of the outer part of the molecule is well overlap with the absorption spectrum of oligoanilines fragment internal parts.

The principles mentioned in the formulas (II-a)-(II-K) sign * (asterisk)are points of connection, in which the structural fragments (II-a)-(II-K) are related to each other in the form of linear conjugated oligomeric chains Arn(or Xmor Qkor ends of chains Arn(or Qkassociated with silicon atoms at the points of branching, or the ends of the chains Arnassociated with apical substituents R.

Schematic representation of the branched oligoanilines presented in figure 1, where the oval marked the inner part of the molecule, and triangles. Possible spatial arrangement of structural fragments oligoanilines General formula (I) corresponds to the one presented in figure 2, where the branching points are the silicon atoms, which are interconnected fragments Arnand Xm(Qk)2

Figure 2 presents a schematic representation of a branched oligoanilines different generations. This branched oligoaniline lane is the second generation (G=1) in the formula (I) corresponds to L=1; branched oligoaniline second generation (G=2) in the formula (I) corresponds to L=3; branched oligoaniline third generation (G=3) in the formula (I) corresponds to L=7.

Preferred examples of R are linear or branched C1-C20alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, m-butyl, isobutyl, terbutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl; C2-C20alkeneamine group, for example 4-butene-1-yl, 5-penten-1-yl, 6-HEXEN-1-yl, 8-octene-1-yl, 11-undecan-1-yl. The most preferred examples of R include ethyl, n-hexyl, n-octyl, 2-ethylhexyl.

Preferred examples of Ar are unsubstituted, thienyl-2,5-diyl General formula (II-a), where R1=R2=N; substituted thienyl-2,5-diyl General formula (II-a), where R1=N, in particular 3-methylthieno-2,5-diyl, 3-utiltity-2,5-diyl, 3-proprtional-2,5-diyl, 3-butylstannyl-2,5-diyl, 3-petitioner-2,5-diyl, 3-exertional-2,5-diyl, 3-(2-ethylhexyl)thienyl-2,5-diyl; unsubstituted phenyl-1,4-diyl General formula (II-b), where R3=R4=N; substituted phenyl-1,4-diyl General formula (II-b), where R3=N, in particular (2,5-dimethyl)phenyl-1,4-diyl, (2,5-diethyl)phenyl-1,4-diyl, (2.5-dipropyl)phenyl-1,4-diyl, (2,5-dibutil)phenyl-1,4-diyl, (2,5-diphenyl)FeNi who -1,4-diyl, (2.5-dihexyl)phenyl-1,4-diyl 2,5-bis(2-ethylhexyl)phenyl-1,4-diyl, (2,5-dimethoxy)phenyl-1,4-diyl, (2,5-diethoxy)phenyl-1,4 - diyl, (2,5-dipropoxy)phenyl-1,4-diyl, (2,5-disoproxil)phenyl-1,4-diyl, (2,5-dibutoxy)phenyl-1,4-diyl, (2,5-dimentions)phenyl-1,4-diyl, (2,5-degeneracy)phenyl-1,4-dial 2,5-bis(2-ethylhexyloxy)phenyl-1,4-diyl. The most preferred examples of Ar: an unsubstituted thienyl-2,5-diyl and unsubstituted phenyl-1,4-diyl.

In the context of this invention under Arnmeans any combination of n links of the same or different Ar selected from the above range. Preferred examples of such combinations are n identical unsubstituted thienyl-2,5-vilnyh fragments connected with each other at positions 2 and 5, for example 2,2'-bithienyl-2,5'-diyl (II-a-1), 2,2':5',2"-tertiary-2,5-diyl (II-a-2):

Another preferred example of such combinations are the combination of various unsubstituted thienyl fragments connected with each other at positions 2 and 5, and various 2,5-substituted phenyl-1,4-vilnyh fragments connected with each other in positions 1 and 4 so that their total number is n, for example fragments represented by formulas (II-1)to(II-12):

P and that n=2 corresponds to formula (II-1), n=3 corresponds to any one of formulas (II-2)to(II-4).

In the context of this invention under Qkmeans any combination of k links of the same or different Q selected from the above range. Preferred examples of such combinations are the unsubstituted thienyl-2,5-diyl (II-a-3), unsubstituted phenyl-1,4-diyl (II-b-1), k equal the unsubstituted thienyl-2,5-vilnyh fragments connected with each other at positions 2 and 5, for example 2,2'-bithienyl-2,5'-diyl (II-a-1), 2,2':5',2"-tertiary-2,5-diyl (II-a-2):

In the context of this invention, Xmmeans any combination of m links of the same or different X is selected from the above range.

Preferred examples of such links are unsubstituted phenyl-1,4-diyl (II-b-1), substituted phenyl-1,4-diyl (II-b-2), the unsubstituted thienyl-2,5-diyl (II-a-3), anthracene-9,10-diyl (II-d), 1,3,4-oxadiazol-2,5-diyl (II-e).

In the context of this invention, Xm(Qk)2means any combination of m links of the same or different X and k parts of equal or different Q selected from the above series. Preferred examples of a combination of such links are: 1,4-phenylenebis(2,2'-beteen-5',5-diyl) (II-5), 2,5-dimethyl-1,4-phenylenebis(2,2'-beteen-5',5-d is silt) (II-6), anthracene-9,10-diylbis(phenylene-1,4-diyl) (II-7), anthracene-9,10-diylbis(Tien-2,5-diyl) (II-8), 2,2'-[1,4-phenylenebis(1,3-oxazol-2,5-guilfoyle-4,1-diyl (II-9):

The principles mentioned in the formulas (II-a-1)to(II-a-3) and (II-1)to(II-9) sign * (asterisk)are points of connection, in which the structural fragments (II-a)-(II-K) are related to each other in the form of linear conjugated oligomeric chains ArnXmQkor the ends of the chains Arnor Xm(Qk)2related to silicon atoms at branching points or with integral substituents R.

Presents the values of R, Ar, Arn, Q, QkX, Xmare particular cases and do not exhaust all possible values and all possible combinations of n, m, k values Ar, Q, X between them.

In particular, in the formula (I) Ar can mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), then the General formula is as follows:

where X, Q, R, R1, R2, L, n, m, k have the above values.

In particular, in the formula (I) X can mean phenyl-1,4-diyl selected from the series (II-b), with the proviso that Q means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), m is 1, k is 2, then the General formula imeediately:

where Ar, R, R1, R2, R3, R4, L, n have the above values.

In this case, for example, when Ar=unsubstituted thienyl-2,5-diyl, R=C6H13R1=R2=R3=R4=N, L=1, n=2 branched oligoaniline first generation with integral hexylene groups (figure 4) can be represented by formula (I-1):

In particular, in the formula (I) X can mean anthracene-9,10-diyl (II-d), with the proviso that Q means phenyl-1,4-diyl selected from a series of compounds of the formula (II-b), m is 1, k is 1, then the General formula is as follows:

where Ar, R, R3, R4, L and n have the above values.

In this case, for example, when Ar=unsubstituted thienyl-2,5-diyl, R=C6H13R3=R4=N, L=1, n=2 branched oligoaniline first generation with integral hexylene groups (figure 5) can be represented by formula (I-2):

In particular, in the formula (I) n can be equal to 2, the General formula is as follows:

where R, Ar, X, Q, L, k and m have the above values.

Particular cases of the formula (I-g) are also dendrimer I-1 (when X=phenyl-1,4-diyl (II-b), Q=Ar=thienyl-2,5-diyl (II-a), R=C6H13, R1=R2=R3=R4=N, L=1, m=1, k=2) and Dendron the p I-2 (at X=anthracene-9,10-diyl (II-d), Q=phenyl-1,4-diyl (II-b), AG=thienyl-2,5-diyl (II-a), R=C6H13, R1=R2=R3=R4=N, L=1, k=m=1).

In particular, for branched oligoanilines first generation L is 1, and for them the formula (I) takes the following form:

where R, Ar, X, Q, k, n and m have the above values.

Particular cases of the formula (I-g) are also dendrimer I-1 (when X=phenyl-1,4-diyl (II-b), Q=Ar=thienyl-2,5-diyl (II-a), R=C6H13, R1=R2=R3=R4=N, m=1, k=n=2) and dendrimer 1-2 (when X=anthracene-9,10-diyl (II-d), Q=phenyl-1,4-diyl (II-b), Ar=thienyl-2,5-diyl (II-a), R=C6H13, R1=R2=R3=R4=N, k=m=1, n=2).

In particular, for branched oligoanilines second generation L is 3, and for them the formula (I) takes the following form:

where R, Ar, X, Q, k, n and m have the above values.

In this case (for example, when X=phenyl-1,4-diyl (II-b), Q=AG=thienyl-2,5-diyl (II-a), R=C6H13, R1=R2=R3=R4=N, m=1, k=n=2) extensive oligoaniline second generation with integral hexylene groups (6) can be represented by formula (I-3):

Declared branched oligoaniline contain the same or different aryl or heteroarylboronic groups with efficient luminescence. This can be is illustrated by the spectra of the absorption and luminescence their diluted solutions (see, for example, Fig.7, 8). Optical characteristics of a series of branched oligoanilines presented in the table. As seen from the above spectral data, the claimed extensive oligoaniline have a broad absorption spectrum, characterized by two peaks, a high quantum yield of luminescence and efficient intramolecular energy transfer. Under high quantum yield in the context of this invention refers to a quantum yield of luminescence of the diluted solution is not less than 30%, mainly not less than 50%. Under the effective intramolecular energy transfer refers to the efficiency of not less than 70%, mainly not less than 90%. These are only examples and in no way limit the characteristics stated branched oligoanilines.

A distinctive feature of the claimed oligoaniline is their high thermal stability, defined in this invention as the temperature of 1% weight loss when heated substance in argon. The temperature for different instantiations is not less than 200°C., preferably not less than 400°C. Data of thermogravimetric analysis (TGA), illustrating the high thermostability of the claimed oligoanilines for example, compounds I-1, I-2 and I-3, shown in Fig.

The problem is solved so the e same time, developed a method of obtaining a branched oligoanilines General formula (I)consists in the fact that the compound of General formula (III)

where Y represents the residue of boric acid or its ester, or Br, or I,

R, Ar, Q, n, k and L have the above values,

interact in the conditions of the Suzuki reaction with a reagent of General formula (IV)

where And means

Br or I, provided that Y represents the residue of boric acid or its ester,

or

the remainder of boric acid or its ester, provided that Y represents Br or I.

X, and m have the above values.

Under Suzuki reaction refers to the interaction of the aryl - or heteroarylboronic with aryl - or heteroarylboronic connection (Suzuki, Chem. Rev. 1995. V.95. R-2483) in the presence of a base and of a catalyst containing a metal of the eighth subgroup. As is known, this reaction as the base can be any base, such as hydroxides, for example NaOH, KOH, LiOH, Ba(OH)2Ca(OH)2; alkoxides, such as NaOEt, KOEt, LiOEt, NaOMe, KOMe, LiOMe; alkali metal salts of carbonic acid, such as carbonates, bicarbonates, acetates, citrates, acetylacetonates, glycine chelates of sodium, potassium, lithium or carbonates of other metals, such as Cs2CO3Tl2CO3; phosphates such as sodium phosphate, potassium, whether the Oia. The preferred base is sodium carbonate. The base used in the form of aqueous solutions or suspensions in organic solvents, such as toluene, dioxane, ethanol, dimethylformamide, or their mixtures. Preferred aqueous solutions of bases. Also in the Suzuki reaction as catalysts can be any suitable compounds containing metals of the eighth subgroup of the periodic table. The preferred metals are Pd, Ni, Pt. The most preferred metal is Pd. The catalyst or catalysts are preferably used in quantities of from 0.01 mol. % to 10 mol. %. The most preferred amount of catalyst is from 0.5 mol. % to 5 mol. % relative to the molar amount of compounds with a lower molar mass, reacts. Most available catalysts are complexes of metals of the eighth subgroup. In particular, stable in air complexes of palladium (0), palladium complexes, recovering directly in the reaction vessel ORGANOMETALLIC compounds (alkyl lithium or magnetogenesis compounds) or phosphine to palladium (0), such as complexes of palladium (2) with triphenylphosphine or other phosphines. For example, PdCl(PPh3)2, PdBr2(PPh3)2Pd(OAc)2or their mixture with triphenylphosphine. Preferably use is to use commercially available Pd(PPh 3)4with or without adding additional phosphines. As phosphines, it is preferable to use the PPh3, PEtPh2, PMePh2, PEt2Ph PEt3. The most preferred triphenylphosphine.

The General scheme of the process can be represented as follows:

where A, X, Y, Q, Ar, R, n, m, k and L have the above values.

In particular, Y in the compound of formula (III) may mean residue cyclic ester of boric acid - 4,4,5,5-tetramethyl-1,3,2-dioxaborolan General formula (V)

then branched oligoaniline receive the following General scheme:

where A, X, Q, Ar, R, n, m, k and L have the above values.

In particular, Ar in the compound of formula (III) may mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), then branched oligoaniline receive the following General scheme:

where A, X, Y, Q, R, R1, R2, n, m, k and L have the above values.

In particular, in the compound of formula (IV) And may indicate a Br, then branched oligoaniline receive the following General scheme:

where X, Y, Q, Ar, R, n, m, k and L have the above values.

In particular, in the compound of formula (IV) X can mean phenyl-1,4-diyl selected from ovarian cancer is and (II-b), with the proviso that the radicals Ar and Q mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), then branched oligoaniline receive the following General scheme:

where A, Y, R, R1, R2, R3, R4, L, k, n, m have the above values.

In particular, in the compound of formula (IV) X can mean anthracene-9,10-diyl (II-d), with the proviso that the radical Q means phenyl-1,4-diyl selected from a series of compounds of the formula (II-b), m is 1, k is 1, then branched oligoaniline receive the following General scheme:

where A, Y, Ar, R, R3, R4, L, n have the above values.

In particular, n in the compound of formula (III) may be equal to 2, then branched oligoaniline receive the following General scheme:

where A, X, Y, Q, Ar, R, L, k and m have the above values.

In particular, L in the compound of formula (III) may be equal to 1, then branched oligoaniline receive the following General scheme:

where A, X, Y, Q, Ar, R, n, k and m have the above values.

In particular L in the compound of formula (III) may be equal to 3, then branched oligoaniline receive the following General scheme:

where A, X, Y, Q, Ar, R, n, k and m have the above values.

In Sopianae interaction can be performed in organic solvents or mixtures of solvents, not interacting with reactive agents. For example, the reaction may be carried out in a medium of an organic solvent, selected from a number of ethers include tetrahydrofuran, dioxane, dimethyl ether of ethylene glycol, diethyl ether of ethylene glycol, dimethyl ether of diethylene glycol; or from a number of aromatic compounds: benzene, toluene, xylene, or from a number of alkanes: pentane, hexane, heptane, or from a number of alcohols: methanol, ethanol, isopropanol, butanol, or from a number of aprotic polar solvents include dimethylformamide, dimethylsulfoxide. A mixture of two or more solvents can also be used. The most preferred solvents - toluene, tetrahydrofuran, ethanol, dimethylformamide or a mixture thereof. Thus the interaction of the source components can be carried out at a temperature in the range from +20°C to +200°C at a stoichiometric molar ratio of functional groups of the starting components or excess of one of them. Preferably, the interaction is carried out at a temperature in the range from +40°C to +150°C. Most preferably, the interaction is carried out at a temperature in the range from +60°C up to +120°C.

After the reaction the product produce by known methods. For example, add water and an organic solvent. The organic phase is separated, washed with water until neutral and dried, after which rest ritel evaporated. As the organic solvent can be used any not miscible or partially miscible with water, the solvent, for example, selected from a number of esters: diethyl ether, methyl tertiary butyl ether, or selected from a number of aromatic compounds: benzene, toluene, xylene, or selected from a number chlororganics connections: dichloromethane, chloroform, carbon tetrachloride, chlorobenzene. For selections, you can use a mixture of organic solvents. The selection of product can be produced without the use of organic solvents, for example, distillation of the solvent from the reaction mixture, separation of the product from the aqueous layer by filtration, centrifugation, or any other known method.

Purification of the crude product is carried out by any known method, such as preparative chromatography in adsorption or exclusive mode, recrystallization, fractional precipitation, fractional dissolution or any combination.

The purity and structure of the synthesized compounds confirm the set data of physico-chemical analysis, well known in the art, such as chromatography, spectroscopy, mass spectroscopy, elemental analysis. The most preferred confirmation of the purity and structure of the branched oligoaniline is the tsya NMR spectra of the nuclei 1H,13C and29Si, as well as civil. Curves civil branched oligoanilines correspond to narrow monodisperse distribution of molecular weight (see, for example, Fig.9-11).

Figure 1 presents a schematic representation of a branched oligoanilines.

Figure 2 presents a schematic representation of a branched oligoanilines different generations G (G=1, 2, or 3 for extensive oligoanilines first, second and third generations, respectively).

Figure 3 presents a schematic representation of the compounds of General formula (III) different generations G (G=1, 2, or 3 for the compounds (III) first, second and third generations, respectively).

Figure 4 presents a schematic structural formulas branched oligoaniline first generation I-1.

Figure 5 presents a schematic structural formulas branched oligoaniline first generation I-2.

Figure 6 presents a schematic structural formulas branched oligoaniline second generation I-3.

Figure 7 presents absorption spectra (a) and luminescence (b) a dilute solution of oligoaniline I-1 in THF.

On Fig presents absorption spectra (a) and luminescence (b) a dilute solution of oligoaniline I-2 in THF.

Figure 9 presents GPC curve Chistov the compounds I-1.

Figure 10 presents GPC curve of the pure compound I-2.

Figure 11 presents GPC curve of the pure compound I-3.

On Fig presents TGA curves of compounds I-1, I-2 and I-3.

The table lists the optical properties of some branched oligoaniline in dilute solutions, including the maxima of the absorption spectra and luminescence quantum yield of luminescence, characterizing its effectiveness.

The invention can be illustrated by the following examples. Used commercially available reagents and solvents. The source reagent 5-bromo-2,2'-Bethoven and 5-hexyl-2,2'-Bethoven received by known methods (S.Gronowitz, A.-B.-Hornfeldt, Thiophenes, Elsevier Academic press, 2004, pp.755). Other source compounds were obtained according to the following examples. All reactions were carried out in anhydrous solvents in an argon atmosphere.

Synthesis of initial reagents

Example 1. Synthesis of (4-bromophenyl)dichloromethylsilane (VI)

To a solution of 40.00 g (0.17 mol) of 1,4-dibromobenzene with 800 ml of THF was added 67.82 ml (0.17 mol) of a 2.5 M solution of n-utility in hexane at a temperature of -50°C. the Reaction mixture was stirred for two hours, then was added a solution of the ether complex of magnesium bromide, freshly prepared from 4.56 g (0.19 mol) of magnesium and at 34.08 g (0.181 mol) of dibromoethane and 120 ml of diethyl who Fira. Thus obtained Grignard reagent was added to a solution of 150 ml (1.36 mmol) of methyltrichlorosilane in 150 ml of THF at -20°C. After filtration under argon and distillation in vacuo (TKip=57°C/0.12 mbar) received 18.41 g (40% of theoretically possible) connection VI.1H NMR (CDCl3): of 1.02 (s, 3H); to 7.59 (d, 1H, J=1.8 Hz).

Example 2. Synthesis of methyl-(2,2'-beteen-5-yl)dichlorsilane (VII)

The solution 26.30 g (0.107 mol) of 5-bromo-2,2'-bithiophene in 270 ml of dry THF was added to a suspension of 2.71 g (0.113 mol) of magnesium in 10 ml of THF. The resulting Grignard reagent was added to the solution 160.36 g (1.073 mol) of methyltrichlorosilane at a temperature below -50°C. the Reaction mixture was stirred for four hours. The precipitate was filtered, the solvent was distilled. The product was purified by distillation in vacuo (TKip=110°C/0.11 mbar). Output: 21.00 g (70% of theoretically possible).1H NMR (CDCl3, δ, ppm, J/Hz): 1.07 (s, 3H), 7.04 (DD, 1H, J13.7 Hz, J2=4.9 Hz), 7.23-7.30 (overlapping signals, 4H), 7.43 (d, 1H,.J=3.7 Hz).13C NMR (δ in CDCl3): 6.71, 124.97, 125.00, 125.66, 128.02, 131.49, 138.08, 138.14, 145.98.29Si NMR (δ in CDCl3): 11.24.

Example 3. Synthesis of (4-bromophenyl)[bis(5'-hexyl-2,2'-bithienyl-5-yl)]methylsilane (VIII)

To a solution of 4.58 g (18.3 mmol) of 5-hexyl-2,2'-bithiophene in THF was added 7.17 ml (18 mmol) of a 2.5 M solution of n-utility in hexane when the tempo is the atur -78°Spoke which was added 2.42 g (9 mmol) of compound VI. After 15 minutes stirring the reaction mixture upon cooling, the reaction yield was 76% (according to GPC). After the standard selection of reaction and purification method column chromatography the chromatographic output of the pure product was 4.65 g (74% of theoretically possible).1H NMR (250 MHz, δ in CDCl3, TMS/ppm): 0.82-0.93 (overlapping signals, 9H), 1.25-1.45 (overlapping signals, 12H), 1.66 (m, 4H, M=5, J=7.3 Hz), 2.77 (t, 4H,.J=7.3 Hz), 6.66 (DD, 2H, J1=3.7 Hz, J2=1.2 Hz), 6.99 (d, 2H, J=3.7 Hz), 7.18 (DD, 4H, J1=4.9 Hz, J2=1.2 Hz), 7.50 (DD, 4H, J1=12.8 Hz, J2=4.2 Hz).

Example 4. Synthesis of 2,2'-beteen-5-yl[bis(5'-hexyl-2,2'-beteen-5-yl)]methylsilane (IX)

Compound IX was obtained similarly to the method of synthesis of compounds VIII of 15.04 g (57.2 mmol) of 5-hexyl-2,2'-bithiophene, 23.55 ml of a 2.5 M solution of n-utility (57.2 mmol) in hexane, 7.99 g (28.6 mmol) of compound VII and 400 ml of THF. After 30 minutes stirring the reaction mixture, the reaction yield was 98% (according to GPC). After extraction and purification was obtained 18.20 g (90% of theoretically possible) chromatographically pure compounds IX.1H NMR (DMSO-CCl4, δ, ppm, J/Hz): 0.88 (t, 6N, J=6.7 Hz), 0.92 (s, 3H), 1.24-1.40 (overlapping signals, N), 1.64 (m, 4H, M=5, J=7.3 Hz), 2.76 (t, 4H, J=7.3 Hz), 6.69 (d, 2H, J=3.05 Hz), 7.01 (d, 1H, J=3.05 Hz), 7.03 (d, 2H, J=3.7 Hz), 7.21 (d, 2H, J=3.7 Hz), 7.26 (d, 1H, J=3.7 Hz), 7.29 (d, 2H, J=3.7 Hz), 7.31 (d, 2H,J=3.7 Hz), 7.37 (d, 1H, J=3.7 Hz).13With NMR (δ in CDCl3): -0.16, 14.07, 22.56, 28.72, 30.15, 31.52, 31.55, 123.96, 124.26, at 124.35, 124.79, 124.82, 125.12, 127.83, 132.96, 134.05, 134.30, 136.97, 137.78, 137.81, 144.47, 145.17, 145.94.29Si NMR (δ in CDCl3): -25.27. Found for C37H42S6Si (%): 62.59; H 5.89; S 27.17; Si 3.69. Calculated (%): 62.84; H 5.99; S 27.20; Si 3.97.

Example 5. Synthesis of [[2,2'-beteen-5-yl(methyl)silander]bis(2,2,-biotene-5',5-diyl)]bis[bis(5'-hexyl-2,2'-beteen-5-yl)(methyl)silane] (X)

Compound X was obtained similarly to the method of synthesis of compound IX from 16.20 g (22.90 mmol) of compound IX, 9.16 ml of a 2.5 M solution of n-utility (22.90 mmol) in hexane, 3.20 g (11.45 mmol) of compound VII and 450 ml of THF. After 60 minutes of stirring the reaction mixture, the reaction yield was 90% (according to GPC). After extraction and purification was obtained 15.00 g (81% of theoretically possible) chromatographically pure compound X.1H NMR (δ in DMSO-CCl4, TMS/ppm): 0.87 (t, N, J=6.7 Hz), 0.91 (s, 6N), 0.94 (s, 3H), 1.22-1.39 (overlapping signals, 24N), 1.63 (m, 8 H, M=5,.J=7.3 Hz), 2.75 (t, 8H, J=7.3 Hz), 6.68 (d, 4H, J=3.7 Hz), 7.00 (d, 1H, J=3.7 Hz), 7.03 (d, 4H, J=3.7 Hz), 7.20 (d, 4H, J=3.7 Hz), 7.24 (d, 1H, J=3.7 Hz), 7.28 (d, 4H, J=3.7 Hz), 7.30-7.35 (overlapping signals, 6N), 7.35-7.40 (overlapping signals, 5H).13With NMR ('s in CDCl3): -0.24, -0.19, 14.07, 22.55, 28.71, 30.14, 31.50, at 31.54, 123.97, here is 124.34, 124.81, 125.15, 125.67, 125.69, 127.82, 132.87, 133.61, 134.26, 134.28, 134.74, 136.90, 137.82, 137.88, 137.91, 143.91, 144.12, 145.18, 145.92.29Si (δ in CDCl3): -25.23, -5.08. Found for C83H90S14Si3(%): 61.39; H 5.64; S 27.60; Si 5.08. Calculated (%): at 61.51; H 5.60; S 27.70; Si 5.20.

Example 6. Synthesis of bis(5'-hexyl-2,2'-beteen-5-yl)(methyl)[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]silane (III-1)

To a solution of 1.63 g of compound VIII in 60 ml THF was pricipally 1.41 ml of a 1.6 M solution of BuLi in hexane, maintaining the temperature below -90°C. is Then added 0.48 ml of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolan. The temperature rises to room temperature and added to 200 ml of distilled water, 300 ml of diethyl ether and 2 ml of 1N HCl solution. After the standard selection of reaction and purification method column chromatography the chromatographic output of the pure product was 1.39 g (82% of theoretically possible).1H NMR (250 MHz, δ in CDCl3, TMS/ppm): 0.82-0.93 (overlapping signals, N), 1.25-1.45 (overlapping signals, 24 H), 1.66 (m, 4H, M=5, J=7.3 Hz), 2.77 (t, 4H, J=7.3 Hz), 6.66 (d, 2H, J=3.7 Hz), 6.99 (d, 2H, J=3.1 Hz), 7.18 (DD, 4H, J16.1 Hz, J2=3.1 Hz), 7.64 (d, 2H, J=7.9 Hz), 7.82 (d, 2H, J=7.9 Hz).

Example 7. Synthesis of bis(5'-hexyl-2,2,-beteen-5-yl)(methyl)[5'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-beteen-5-yl]silane (III-2)

The compound III-2 was obtained similarly to the method of synthesis of compound III-1 of 2.00 g (2.8 mmol) of the compound IX, 1.77 ml of a 1.6 M solution of n-utility (2.80 mmol) in hexane, 0.58 ml (2.8 mmol) of 2-isop is epoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 75 ml of THF. After extraction and purification was obtained 2.32 g of chromatographically pure compound III-2. MS m/z 833 (M+calculated 833.18).1H NMR (δ in DMSO-CCl4, TMS/ppm): 0.87 (6N, t, J=6.7 Hz), 0.93 (3H, s), 1.23-1.38 (24N, overlapping peaks), 1.62 (4H, m), M=5, J=7.3), 2.76 (4H, t, J=7.7 Hz), 6.72 (2H, d, J=3.1 Hz), 7.07 (2H, d, J=3.7 Hz), 7.24 (2H, d, J=3.7 Hz), 7.31 (2H, d, J=3.7 Hz), 7.35 (2H, t, J=3.1 Hz), 7.43 (2H, t, J=3.1 Hz).13With NMR (125 MHz, CDCl3): -0.18, 14.07, 22.56, 24.76, 28.72, 30.16, 31.52, 31.55, 84.17, 123.99, at 124.35, 124.82, 125.51, 125.80, 132.85, 134.29, 134.85, 137.84, 137.90, 143.61, 144.24, 145.20, 145.95. Found for C43H53BO2S6Si (%): 62.00; H 6.40; S 23.04; Si 3.17. Calculated: C, 61.99; H 6.41; S 23.09; Si 3.37.

Example 8. Synthesis of [{methyl[5'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-beteen-5-yl]silander}bis(2,2'-biotene-5',5-diyl)]bis[bis(5'-hexyl-2,2,-beteen-5-yl)(methyl)silane] (III-3)

The compound III-3 was obtained similarly to the method of synthesis of compound III-1 of 1.1 g (0.7 mmol) of compound X, 0.41 ml of a 1.6 M solution of n-utility (0.7 mmol) in hexane, 0.14 ml (0.7 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 35 ml of THF. After extraction and purification was obtained 1.14 g of chromatographically pure compound III-3.1H NMR (δ in DMSO-CCl4, TMS/ppm): 0.87 (t, N, J=6.7 Hz), 0.91 (s, 6N), 0.94 (s, 3H), 1.22-1.39 (overlapping signals, 24N), 1.62 (m, 8H, M=5, J=7.3 Hz), 2.75 (t, 8H, J=7.3 Hz), 6.69 (4H, d, J=3.1 Hz), 7.03 (4H, d, J=3.7 Hz), 7.20 (4H, d, J=3.1 Hz), 7.28 (4H, d, J=3.7 Hz), 7.30-7.35 (overlapping igaly, 6N), 7.39 (4H, d, J=3.7 Hz), 7.43 (1H, d, J=3.7 Hz).

Synthesis of branched oligoanilines.

General methods of synthesis of branched oligoanilines: to a solution of 1.0 mmol of compound III in toluene was added 0.45 mmol of compound IV, 0.05 mmol catalyst containing metals of the eighth subgroup of the periodic table, and 3.0 mmol of substrate. Stirred for several hours at a temperature of 80°C.-120°C. After the reaction the product produce by known methods. The product was then purified by the method of column chromatography on silica gel.

Example 9. Synthesis of branched oligoaniline (I-1)

Extensive oligoaniline I-1 was obtained according to the General method of synthesis of 1.12 g of compound III-2, 0.15 g of 1,4-dibromophenol, 0.077 g of the catalyst Pd(PPh3)4, 2 ml of a 2M solution of Na2CO3in water and 20 ml of toluene. After extraction and purification was obtained 0.46 g (50% of theoretically possible) clean branched oligoaniline (I-1).1H NMR (250 MHz, δ in DMSO-CCl4, TMS/ppm):: 0.88 (t, N, J=6.7 Hz), 0.93 (s, 6N), 1.25-1.45 (overlapping signals, 24 H), 1.63 (m, 8H, M=5, J=7.3 Hz), 2.76 (t, 8H, J=7.3 Hz), 6.70 (d, 4H, J=3.7 Hz), 7.05 (d, 4H, J=3.7 Hz), 7.23 (d, 4H, J=3.1 Hz), 7.28 (d, 2H, J=3.7 Hz), 7.31 (d, 4H, J=3.7 Hz), 7.36 (DD, 4H, J1=7.3 Hz, J2=3.7 Hz), 7.43 (d, 2H, J=3.7 Hz), 7.63 (s, 4H).

Example 10. Synthesis of branched oligoaniline (I-2)

Do is run oligoaniline I-2 was obtained according to the General method of synthesis of 1.23 g of compound III-1, 0.23 g of 9,10-dibromoanthracene, 0.096 g of the catalyst Pd(PPh3)4, 2.5 ml of 2M solution of Na2CO3in water and 30 ml of toluene. After extraction and purification was obtained 0.937 g (97% of theoretically possible) clean branched oligoaniline (I-2).1H NMR (250 MHz, δ in CDCl3, TMS/ppm): 0.88 (t, N, J=6.7 Hz), 1.03 (s, 6N), 1.25-1.45 (overlapping signals, 24 H), 1.63 (m, 8H, M=5, J=7.3 Hz), 2.78 (t, 8H, J=7.3 Hz), 6.69 (d, 4H, J=3.7 Hz), 7.06 (d, 4H, J=3.7 Hz), 7.24 (d, 4H, J=3.7 Hz), 7.28-7.37 (overlapping signals, 8H), 7.51 (d, 4H, J=7.9 Hz), 7.69 (d, 2H, J=3.1), 7.72 (d, 2H, J=3.1 Hz), 7.87 (d, 4H, J=7.9 Hz).

Example 11. Synthesis of branched oligoaniline (I-3)

Extensive oligoaniline I-3 was obtained according to the General method of synthesis of 1.05 g of compound III-3, 0.057 g of 1,4-dibromophenol, 0.035 g of the catalyst Pd(PPh3)4, 1 ml of 2M solution of Na2CO3in water and 15 ml of toluene. After extraction and purification was obtained 0.343 g (43% of theoretically possible) clean branched oligoaniline (I-3).1H NMR (δ in DMSO-CCl4, TMS/ppm): 0.89 (t, 24N, J=6.7 Hz), 0.92 (s, N), 0.94 (s, 6N), 1.22-1.45 (overlapping signals, N), 1.66 (m, 16 H, M=5, J=7.3 Hz), 2.77 (t, N, J=7.3 Hz), 6.62 (8H, d, J=3.7 Hz), 6.97 (8H, d, J=3.7 Hz), 7.14 (8H, d, J=3.7 Hz), 7.19 (2H, d, J=3.7 Hz), 7.22-7.35 (overlapping signals, N), 7.57 (4H, s).

Table
Extensive oligoaniline and the retrieval method
OligoanilineSolventThe maximum of the absorption spectrum, nmThe maximum of the luminescence spectrum, nmQ%E%
1-1THF334/404456/4855599±1
1-2THF261/333/375/396418/4318175±5
1-3THF334/404456/4855590±2
Note: Q is the quantum yield of luminescence, E - efficiency of intramolecular energy transfer.

1. Extensive oligoaniline General formula (I),

where R is the Deputy of a range of: linear or branched C1-C20alkyl group; a linear or branched C1-C20alkyl groups, divided what about the at least one oxygen atom; linear or branched C1-C20alkyl groups separated by at least one sulfur atom; a branched C3-C20alkyl groups separated by at least one atom of silicon; C2-C20alkeneamine group,
Ar represents the same or different allenbyi or heteroarenes radicals selected from the series of: substituted or unsubstituted thienyl-2,5-diyl General formula (II-a)

substituted or unsubstituted phenyl-1,4-diyl General formula (II-b),

substituted or unsubstituted 1,3-oxazol-2,5-diyl General formula (II-b)
substituted fluoren-4,4'-diyl General formula (II-g)

substituted cyclopentadiene-2,7-diyl General formula (II-d)

where R1, R2, R3, R4, R5independently of one another denote H or a Deputy of the above series for R; R6, R7, R8, R9means the Deputy of the above series for R,
Q denotes a radical of the above number for Ar,
X represents at least one radical selected from the above number for Ar and/or a radical from the series: 2,1,3-benzothiadiazole-4,7-diyl General formula (II-e)

anthracene-9,10-diyl formula (II-g)

1,3,4-oxadiazol-2,5-diyl General formula (II-C)

1-phenyl-2-pyrazolin-3,5-diyl General formula (II)
perylene-3,10-diyl General formula (II)
.
L is 1 or 3 or 7, preferably 1 or 3;
n means an integer from the range from 2 to 4,
m means an integer from the range from 1 to 3,
k denotes an integer from the range from 1 to 3.

2. Extensive oligoaniline according to claim 1, wherein Ar means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a).

3. Extensive oligoaniline according to claim 1, characterized in that X represents phenyl-1,4-diyl selected from the series (II-b), with the proviso that Q means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a), m is 1, k is 2.

4. Extensive oligoaniline according to claim 1, characterized in that X represents the anthracene-9,10-diyl (II-d), with the proviso that Q means phenyl-1,4-diyl selected from a series of compounds of the formula (II-b), m is 1, K is 1.

5. Extensive oligoaniline according to any one of claims 1 to 4, characterized in that n is equal to 2.

6. Extensive oligoaniline according to any one of claims 1 to 4, wherein L is 1.

7. Extensive oligoaniline according to any one of claims 1 to 4, characterized in that L is equal to 3.

8. Extensive oligoaniline according to any one of claims 1 to 4, characterized in that they have a quantum yield of luminescence is not m is it 30%, mainly not less than 50%.

9. Extensive oligoaniline according to any one of claims 1 to 4, characterized in that they possess intramolecular energy transfer efficiency not less than 70%, mostly at least 90%.

10. Extensive oligoaniline according to any one of claims 1 to 4, characterized in that they are thermally stable up to a temperature of at least 200°C., preferably not less than 400°C.

11. A method of obtaining a branched oligoanilines according to any one of claims 1 to 10, which consists in the fact that compounds of General formula (III)

where Y represents the residue of boric acid or its ester or Br or I,
R, Ar, Q, n, k and L have the above values,
interact in the conditions of the Suzuki reaction with a reagent of General formula (IV)
,
where And means:
Br or I, provided that Y represents the residue of boric acid or its ester, or
the remainder of boric acid or its ester, provided that Y represents Br or I;
X and m have the above values.

12. The method according to claim 11, characterized in that the ester of boric acid is an ester selected from the range: 4,4,5,5-tetramethyl-1,3,2-dioxaborolan General formula (V-a)
1,3,2-dioxaborolan General formula (V-b)

1,2,3-dioxaborinane General formula (V-in)

5,5-dimethyl-1,2,3-dioxaborolan General formula is (V-g)

13. The method according to claim 11, characterized in that the compound of formula (III) Ar means thienyl-2,5-diyl selected from a series of compounds of the formula (II-a).

14. The method according to claim 11, wherein in the compound of formula (IV) means Br.

15. The method according to claim 11, characterized in that X in the compound of formula (IV) means phenyl-1,4-diyl selected from the series (II-b), with the proviso that the radicals Ar and Q mean thienyl-2,5-diyl selected from a series of compounds of the formula (II-a).

16. The method according to claim 11, characterized in that X in the compound of formula (IV) means anthracene-9,10-diyl (II-d), with the proviso that the radical Q means phenyl-1,4-diyl selected from a series of compounds of the formula (II-b), m is 1, k is 1.

17. The method according to any of § § 11 to 16, characterized in that the compound of formula (III), n is 2.

18. The method according to any of § § 11 to 16, characterized in that the compound of formula (III) L is equal to 1.

19. The method according to any of § § 11 to 16, characterized in that the compound of formula (III) L is equal to 3.

20. The method according to any of § § 11 to 16, characterized in that the interaction of the components is carried out at a temperature from 20 to 200°C., preferably at a temperature of from 60 to 120°C.

21. The method according to any of § § 11 to 16, characterized in that the interaction of components is carried out in a medium of an organic solvent selected from a range of toluene, tetrahydrofuran, ethanol, dimethylformamide or mixtures thereof.

22. With the persons in any of § § 11-16, characterized in that the branched oligoaniline have a quantum yield of luminescence of at least 30%, mainly not less than 50%.

23. The method according to any of § § 11 to 16, characterized in that the branched oligoaniline possess intramolecular energy transfer efficiency not less than 70%, mostly at least 90%.

24. The method according to any of § § 11 to 16, characterized in that the branched oligoaniline thermally stable up to a temperature of at least 200°C., preferably not less than 400°C.



 

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9 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention concerns fluorescent bleach containing a mix of two asymmetrically substituted and one symmetrically substituted triazinylaminostilbene disulfone acid, a new symmetrically substituted derivative, method of their obtaining, and application of the mix in synthetic or natural organic material (especially paper) bleaching and in fluorescent bleaching and sun resistance boost of textile.

EFFECT: high substantivity and light resistance of the claimed fluorescent bleaches and their mixes, and better water solubility of the claimed mixes in comparison to the solubility of each individual bleach.

15 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of chemical technology of silicon-organic compounds. Technical task lies in synthesis of novel polyarylsilane links including dendrimers of large generations suitable for application as luminescent materials for organic electronics and photonics. Claimed are dendrimers of general formula (I) where R1 stands for substituent from group: linear or branched C1-C20alkyl groups; linear or branched C1-C20alkyl groups separated by at least one oxygen atom; linear or branched C1-C20 alkyl groups separated by at least one sulphur atom; branched C3-C20 alkyl groups separated by at least one silicon atom; C2-C20alkenyl groups; Ar represents, independently for each n and m, similar or different arylene radicals, selected from group: substituted or non-substituted thienyl-2,5-diyl of general formula (II-a) substituted or non-substituted phenyl-1,4-diyl of general formula (II-b) substituted or non-substituted 1,3-oxazol-2,5-diyl of general formula (II-c) substituted fluorene-4,4'-diyl of general formula (II-d) where R2, R3, R4, R5, R6 represent independently on each other H or said above for R1; R7 stands for said above for R1; K is equal 2 or 3 or 4; L is equal 1 or 3 or 7 or 15; m and n represent whole numbers from series from 2 to 6. Method of obtaining dendrimers lies in the following: monodendron of general formula (III) where X represents H or Br or I, first reacts with lithiumising agent of general formula R8Li, where R8 represents linear or branched C1-C10alkyl group, dialkylamide or phenyl group; then obtained compound reacts with functional compound selected from group of compounds of formula (CH3)4-KSiYK, where Y represents Cl, or Br, or -OCH3, or -OC2H5, or -OC3H7, or -OC4H9. Claimed method is technological, use of expensive catalysts is not required.

EFFECT: elaboration of technological method of synthesising novel polyarylsilane dendrimers which does not require use of expensive catalysts.

24 cl, 12 dwg, 1 tbl, 13 ex

FIELD: organosilicon polymers.

SUBSTANCE: novel polycyclic poly- and copolyorganocyclocarbosiloxanes with variable cycle size including structural motif of general formula: , wherein (1) x=3 or 4 and y=1, (2) x=2 and y=2, (3) x=3, and suitable as preceramic templates for manufacturing oxygen-free silicon carbide ceramics are prepared by Würtz reaction in toluene via interaction of chloro-derivatives of organocarbosilanes with metallic sodium in the form of suspension.

EFFECT: enlarged assortment of preceramic templates.

2 cl, 1 tbl, 3 ex

FIELD: organosilicon polymers.

SUBSTANCE: polydimethylsilane is obtained by reaction of dimethyldichlorosilane with sodium at 150-170°C followed by decomposition of unreacted sodium with methyl alcohol, isolation of desired polymer, washing on filter with distilled water, drying on air and the in vacuum. Process is characterized by that sodium reagent is added as deposited on water-soluble solid, incombustible, inorganic substrate.

EFFECT: reduced fire risk of synthesis process and labor intensity of polymer isolation stage.

2 dwg, 1 tbl, 5 ex

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR12 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).

EFFECT: improved preparing method.

1 tbl, 9 ex

The invention relates to methods of modifying polydimethylsiloxane rubber, not having in its composition of active groups, UV light and can be used to obtain a new silicon-containing polymers with a wide range of applications, including

The invention relates to a method for SiOH-functional dendrimeric of carbosilane

The invention relates to a method of obtaining new undescribed in the literature polylithium derivatives karbosilanovykh compounds (PLCS), which can find application in the chemical industry as intermediates for various materials organiseorganised

The invention relates to methods of producing organosilicon polymer of polymer of the formula:

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(patent N 4220600, CL

FIELD: chemical technology.

SUBSTANCE: invention describes a method for preparing metallopolycarbosilanes. Method involves interaction of polycarbosilanes with molecular mass above 200 Da and with the main chain consisting of links of the formula: [-(R)2Si-CH2-] wherein R means hydrogen atom (H), (C1-C4)-alkyl or phenyl groups with metalloorganic compounds of the formula MXz wherein M means transient metal of III-VIII group of Periodic system; z = 2-4; X means NR12 wherein R1 means (C1-C4)-alkyl group in organic solvent medium at temperatures from 20°C to 400°C under pressure from 5.05 MPa to 0.2 kPA. Method provides preparing fusible soluble polymers with homogeneous distribution of chemically bound metal atoms that elicit high capacity for fiber- and film-formation from solutions or melts that are hardened in thermochemical treatment and provides high yield of ceramic residue in pyrolysis (up to 85 wt.-%).

EFFECT: improved preparing method.

1 tbl, 9 ex

FIELD: organosilicon polymers.

SUBSTANCE: polydimethylsilane is obtained by reaction of dimethyldichlorosilane with sodium at 150-170°C followed by decomposition of unreacted sodium with methyl alcohol, isolation of desired polymer, washing on filter with distilled water, drying on air and the in vacuum. Process is characterized by that sodium reagent is added as deposited on water-soluble solid, incombustible, inorganic substrate.

EFFECT: reduced fire risk of synthesis process and labor intensity of polymer isolation stage.

2 dwg, 1 tbl, 5 ex

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